Polysilane compound containing perfluoro(poly)ether group

ABSTRACT

wherein: Rf represents monovalent R1f(OC4F8)a—(OC3F6)b—(OC2F4)c—(OCF2)d wherein a, b, c, and d independently represent an integer of from 3 to 200 inclusive, and the sum of a, b, c, and d is at least 1; R1f is fluorinated alkyl group, linear or branched, with 1-4 carbons; Y represents a polyvalent organic group, Q represents a hydrolyzable group, a hydroxyl group, or alkyloxy group and is capable of forming a siloxane bond with Si atoms located at the terminal of the molecular chain of formula (I) or other active sites of the treated surface, Z is a monovalent alkyl group, or hydrogen; p is 1 or 2, w is 2-14, p+w is 3 to 15, and k is from 1 to 3.

BACKGROUND Field of the Invention

The present invention relates to coating compositions comprising apolysilane compound containing perfluoro(poly)ether group and methods ofpreparing the coating.

Description of Related Art

Many plastic or glass surfaces, such as surfaces of display or opticaldevices, are susceptible to contaminations like fingerprints, soil,cosmetics, etc. Various coating materials and technologies have beenproposed to solve the problem and make such surfaces easy to clean.Moreover, the surface coatings need to be durable to resist scratch,wear and rubbing.

Generally, surfaces with high surface energy are more liable to bestained and harder to clean than those with low surface energy.Therefore, there is a need for coatings having low surface energy whichcan be securely attached to the desired surface, such as mobile devices,monitors, eyewear, windows and mirrors.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a coating composition comprising: atleast one fluorinated silane of the formula (I):

(Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w)  (I)

wherein: Rf represents monovalentR¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d) wherein a, b, c, and dindependently represent an integer of from 3 to 200 inclusive, and thesum of a, b, c, and d is at least 1; R¹f is fluorinated alkyl group,linear or branched, with 1-4 carbons; Y represents a polyvalent organicgroup that enables branching and can contain polyvalent alkyl, divalentpolysiloxane, p-, m-, or o-phenylene; Y contains at least 2 or more ofthe heteroatom containing groups selected from: —O—, —S—, —NR²—,—C(O)O—, C(O)NR²—, where R² is covalent bond, divalent alkylene,hydrogen, methyl, ethyl or isopropyl, The valency of Y is 3 or morerepresented by the sum of p+w from 3 to 15, and w is from 2 to 14, and kis from 1 to 3.Polyvalent organic groups Y can be comprised of but not limited to thefollowing examples:—CH₂[—OCH₂CH(—OC₃H₆—)CH₂—]_(e)—OC₃H₆—, where e is from 1 to 4,—CH₂CH₂SCH₂CH(—OC₃H₆—)CH₂OC₃H₆—,—CH₂OCH₂CH(—OC₃H₆—)CH₂N(C₃H₆—)₂,—CH₂[—OCH₂CH(—CH₂OC₃H₆—]_(m)—OC₃H₆—, where m is from 1 to 4,and combinations thereof.The above polyvalent group Y can be further defined as follows:—CH₂[—OCH₂CH(CH₂O-A-O—CH₂CH(—OC₃H₆—)CH₂OC₃H₆—)]_(f)—OC₃H₆—,—CH₂[—OCH₂CH(CH₂O-A-O—CH₂CH(—OC₃H₆—)CH₂OC₃H₆—)]_(f)—O(CH₂CH₂O)_(x)—C₃H₆—,—CH₂[—OCH₂CH(CH₂O-A-O—CH₂CH(—NHC₃H₆—)CH₂OC₃H₆—)]_(f)—OC₃H₆—,—CH₂[—OCH₂CH(CH₂O-A-NH—CH₂CH(—OC₃H₆—)CH₂OC₃H₆—)]_(f)—OC₃H₆—,—CH₂[—OCH₂CH(CH₂O-A-N(CH₂CH(—OC₃H₆—)CH₂OC₃H₆—)₂]_(f)—OC₃H₆—,where A is divalent linear or branched alkylene, or p-, m-, oro-phenylene group. Examples of group A are represented by but notlimited to 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,3-propylene,1,2-propylene, 1,2-ethylene, and neopentylene —CH₂C(CH₃)₂CH₂— groups,and where f is from 1 to 4.

Q represents a hydrolyzable group, a hydroxyl group, or alkyloxy group,and is capable of forming a siloxane bond with other Si atoms located atthe terminal of the molecular chain of formula (I) or other active sitesof a treated surface. The group Q of Formula (I) is exemplified by thefollowing:

—Cl, —OCH₃, —OCH₂CH₃, —OCH(CH₃)₂, —O(CH₂CH₂O)_(x)CH₃, where x is from 1to 10,—[—OSi(CH₃)₂—]_(y)OCH₃, —[—OSi(CH₃)₂-]_(y)OH, —[—OSi(CH₃)₂—]_(y)H,—[—OSi(CH₃)₂-]_(y)CH₃, —[—OSi(OCH₃)₂-]_(y)H, —[—OSiH(OCH₃)—]_(y)OCH₃where y is from 1 to 6,—OSi(CH₃)₂O—Si(OCH₃)₂—C₃H₆—Si(OCH₃)₃, —OSi(CH₃)₂O—Si(OCH₃)₃.Q represents a hydrolyzable group, acyloxy, Iminoxy, dialkylaminogroups, a hydroxyl group, or alkoxy group. Detailed examples of thesegroups can include methoxy (—OCH₃), ethoxy (—OC₂H₅), isopropyloxy(—O-i-C₃H₇), dimethylketoximo (—ON═C(CH₃)₂), acetoxy (—OC(O)CH₃),dimethylamino (—N(CH₃)₂), diethylamino (—N(C₂H₅)₂), and diisopropylamino(—N(i-C₃H₇)₂), p is 1 or 2, and w is 2-14.

Z represents a monovalent alkyl group such as methyl, ethyl, propyl,butyl, phenyl group, or hydrogen.

The present invention also provides a coated article comprising: (a) asupport surface; and (b) a coating comprising at least one fluorinatedsilane moiety of the formula (I) (Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w).

The present invention also provides a coated article comprising: (a) asupport surface; and (b) a coating prepared by applying at least onefluorinated silane of the formula (I) (Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w)onto the support surface; wherein: Rf represents monovalentR¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d) wherein a, b, c, and dindependently represent an integer of from 3 to 200 inclusive, and thesum of a, b, c, and d is at least 1; R¹f is fluorinated alkyl group,linear or branched, with 1-4 carbons; Y represents a polyvalent organicgroup as defined above, Q and Z is as defined above.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows schematic presentations of contact angles. FIG. 1A presentsa typical water contact angle on a hydrophilic surface. FIG. 1B presentsa typical water contact angle on a hydrophobic surface.

DETAILED DESCRIPTION

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims. Other features andbenefits of any one or more of the embodiments will be apparent from thefollowing detailed description, and from the claims.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In case of conflict, thepresent specification, including definitions, will control. Althoughmethods and materials similar or equivalent to those described hereincan be used in the practice or testing of embodiments of the presentinvention, suitable methods and materials are described below. Inaddition, the materials, methods, and examples are illustrative only andnot intended to be limiting.

When an amount, concentration, or other value or parameter is given aseither a range, preferred range or a list of upper preferable valuesand/or lower preferable values, this is to be understood as specificallydisclosing all ranges formed from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range.

Before addressing details of embodiments described below, some terms aredefined or clarified.

The term “an elevated temperature”, as used herein, means a temperaturehigher than the room temperature.

The term “unsaturated fluorocarbon”, as used herein, means anunsaturated partially fluorinated organic molecule.

The term “hydrofluorocarbon”, as used herein, means a moleculecontaining hydrogen, carbon, and fluorine. A hydrofluorocarbon in thisdisclosure can be saturated or unsaturated.

The term “hydrofluoroolefin”, as used herein, means a moleculecontaining hydrogen, carbon, fluorine, and at least one carbon-carbondouble bond.

The term “unsaturated fluorocarbon ether”, as used herein, means amolecule containing carbon, fluorine, at least one carbon-carbon doublebond, and at least one ether functional group.

The term “unsaturated hydrofluorocarbon ether”, as used herein, means amolecule containing hydrogen, carbon, fluorine, at least onecarbon-carbon double bond, and at least one ether functional group.

The term “saturated hydrofluorocarbon ether”, as used herein, means amolecule containing hydrogen, carbon, fluorine, and at least one etherfunctional group.

The term “support surface”, as used herein, means a solid surface ontowhich the coating composition of formula (I) and formula (IV) can beattached via covalent bonding. Typical support surfaces include metaloxides, metal, silica, glass, polymeric materials such as plastic, andany combinations thereof. In some embodiments of this invention, thesupport surface is selected from the group consisting of metal oxides,glass, plastics, and any combinations thereof. In some embodiments ofthis invention, the support surface is a metal oxide. In someembodiments of this invention, the support surface is a plastic. In someembodiments of this invention, the support surface is a glass. In someembodiments of this invention, the support surface is silica.

The term “contact angle”, as used herein, means the angle formed betweenthe liquid/support surface interface and the liquid/air interface. It isillustrated as angle α in FIG. 1. A contact angle can be measured byproviding a drop of liquid (1) on a surface of a substrate (2), lookingat the profile of the liquid, and measuring the angle formed between thesurface and the liquid profile with the vertex at the three-phase (solidsurface, liquid and air) interface point as shown in FIG. 1.

Contact angle measurements can be used to determine the surface energyof a substrate. Generally, a larger contact angle indicates a smallersurface energy.

The present invention provides an antifouling, wear-resistant,anti-scratch, anti-smudge, anti-fingerprint, mold-release coatingcomposition that can be applied to touch panel screens. The compositioncomprises at least one fluorinated silane of the formula (I)(Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w) wherein: Rf represents monovalentR¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d) wherein a, b, c, and dindependently represent an integer of from 3 to 200 inclusive, and thesum of a, b, c, and d is at least 1; R¹f is fluorinated alkyl group,linear or branched, with 1-4 carbons; Y represents a polyvalent organicgroup, with valency of 3 or more, preferred polyvalent organic group Ycan contain polyvalent alkyl, and at least one of the following groups—O—, —S—, —NR²—, examples of polyvalent organic group Y, include forexample—CH₂O[—CH₂CH(—OC₃H₆—)CH₂—O-]_(e)-[CH₂CH(—CH₂OC₃H₆—)—O-]_(m)C₃H₆—,wherein e and m are independently integers from 0 to 4, and e+m is atleast 1, —CH₂CH₂SCH₂CH(—OC₃H₆—)CH₂OC₃H₆—,—CH₂OCH₂CH(—OC₃H₆—)CH₂N(—C₃H₆—)₂, —CH₂OCH₂CH(—OC₃H₆—)—CH₂OCH₂CH(—OC₃H₆—)CH₂OC₃H₆—;

Q represents a hydrolyzable group, a hydroxyl group, or alkyloxy, groupand is capable of forming a siloxane bond with Si atoms located at theterminal of the molecular chain of formula (I) or other active sites ofa treated surface; Z represents a monovalent alkyl group such as methyl,ethyl, propyl, butyl, or a phenyl group, p is 1 or 2, and w is 2-14.

Shown below are additional examples of fluoropolyethers silanesaccording to formula (I):

Where h is from 1 to 4.

wherein e and m are independently integers from 0 to 4, and e+m is atleast 1.

In an aspect of the invention, compounds of formula (I) can be preparedby hydrosylilation reaction from the allyloxy- or allylamino-compoundsof formula (II):

(Rf)_(p)—Y¹—(CH₂CH═CH₂)_(w)  (II)

where Y¹ is polyvalent group, and p and w are defined as in formula (I).

The skilled artisan will readily understand that compounds of formula(II) can be prepared from the corresponding hydroxyl derivatives offormula (III):

(Rf)_(p)—Y¹—(H)_(v)(CH₂CH═CH₂)_(w-v),  (III)

where v is 1-13 and p and was defined in formula (I). Details of suchsynthesis are disclosed, for example, by Howell, et al. in the Journalof Fluorine Chemistry 126 (2005) 281-288.

The present invention also provides a coated article. The coated articlecomprises (a) a support surface; and (b) a coating comprising at leastone fluorinated silane moiety of the formula (I) above, and wherein theat least one fluorinated silane moiety and the support surface arecovalently bonded.

The present invention further provides a coated article which comprises(a) a support surface; and (b) a coating prepared by applying at leastone fluorinated silane of the formula (I)(Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w) onto the support surface; wherein: Rfrepresents monovalent R¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)wherein a, b, c, and d independently represent an integer of from 3 to200 inclusive, and the sum of a, b, c, and d is at least 1; R¹f isfluorinated alkyl group, linear or branched, with 1-4 carbons; Yrepresents a polyvalent organic group, with valency of 3 or more, Qrepresents a hydrolyzable group, a hydroxyl group, or alkyloxy group. Qis capable of forming a siloxane bond with Si atoms located at theterminal of the molecular chain of formula (1); p is 1 or 2, and w is2-14; Z represents monovalent alkyl group such as methyl, ethyl, propyl,butyl, phenyl group, or hydrogen.

It was found through experiments that branched perfluoropolyether (PFPE)oligomers with the formula C₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, where n is aninteger from 7 to 100 are particularly suitable to provide antifoulingcoatings which can be effectively resistant to contamination and easy toclean.

The fluorinated silane of the formula (I)(Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w) can be prepared by processes known inthe art. For example,C₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)CH₂OCH₂CH[OCH₂CH₂CH₂Si(OMe)₃]—CH₂OCH₂CH₂CH₂Si(OMe)₃orC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)CH₂OCH₂CH[OCH₂CH₂CH₂Si(OMe)₃]—CH₂O(CH₂)₄—OCH₂CH[OCH₂CH₂CH₂Si(OMe)₃]—CH₂OCH₂CH₂CH₂Si(OMe)₃can be made from the acyl fluoride C₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)C(O)F,where n is an integer from 7 to 100 using the following procedures: theacyl fluoride can be first transformed to become the correspondingmethyl ester through reactions with methanol; the methyl ester can thenbe reduced by using NaBH₄ or LiAlH₄ to form the corresponding alcoholC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)CH₂OH; the alcohol can then react withglycidol or glycidyl ethers (such as allyl glycidyl ether, diglycidylether, resorcinol diglycidyl ether, 1,4-butanediol diglycidyl ether,tris(2,3-epoxypropyl) isocyanurate, N,N-diglycidyl-4-glycidyloxyaniline,tris(4-hydroxyphenyl)methane triglycidyl ether, trimethylolpropanetriglycidyl ether, 4,4-methylenebis(N,N-diglycidylaniline),1,2-propanediol diglycidyl ether, poly(ethylene glycol) diglycidylether, poly(dimethylsiloxane) diglycidyl ether, and similar) usingsodium hydride to form the mono-adducts as well as branched oligomers ofglycerol and glycidyl ethers as described in European Journal of OrganicChemistry, (5), 875-896; 2001. Example of such chemical pathway isdescribed as follows:

In the case when diglycidyl or triglycidyl compounds are used, one ortwo perfluoropolyether moieties can attach to the diglycidyl ether toform the oxirane-containing perfluoropolyethers of formula (IV):

where each p and j is from 1 to 2, and Rf is as defined above;where L comprises divalent or trivalent group containing at least 1heteroatom such as —O—, —S—, and —N<. Group L can be represented by butnot limited to —O(CH₂)₄O—, —O(CH₂)₂O—, —OC₆H₄O—, —OCH₂C(CH₃)₂CH₂O—,

and j is from 1 to 2.More specific examples of compound of formula (IV) include, for example,

Compounds of formula (IV) of the present invention containingperfluoropolyether and glycidyl groups are capable of forming covalentbond with hydroxyl and amino groups of the treated surface and can beapplied from the diluted solution for the treatment of various surfacesto obtain wear-resistant, antifouling, anti-smudge, or mold-releasecoating, which can be effectively resistant to contamination and easy toclean. Obtained glycidyl derivatives of formula (IV) containing glycidylgroups can be further reacted with allyl alcohol, polyethylene glycolmono-allyl ether, diallyl amine and similar allyl-containing alcohols oramines. The resulting intermediates of formula (III)(Rf)_(p)—Y¹—(H)_(v)(CH₂CH═CH₂)_(w-v), such asC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)CH₂OCH₂CH(OH)—CH₂O(CH₂)₄—OCH₂—CH(OH)—CH₂OCH₂CH═CH₂,containing one or more active hydroxyl groups can be further reactedwith allyl bromide or allyl chloride in the presence of KOH to form thecorresponding poly-allyl ether; the poly-allyl ether of formula (II),and can then be converted to the corresponding trichlorosilane throughreactions with HSiCl₃ in the presence of the Ashby's catalyst; theformed trichlorosilane can then be converted to the final product offormula (I) such asC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)CH₂OCH₂CH[OCH₂CH₂CH₂Si(OMe)₃]—CH₂OCH₂CH₂CH₂Si(OMe)₃,orC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)CH₂OCH₂CH[OCH₂CH₂CH₂Si(OMe)₃]—CH₂O(CH₂)₄OCH₂CH[OCH₂CH₂CH₂Si(OMe)₃]—CH₂OCH₂CH₂CH₂Si(OMe)₃through methoxylation reactions with methanol. Details of the abovesynthesis are also disclosed by Howell, et al. in the Journal ofFluorine Chemistry 126 (2005) 281-288, and by Hervieu, et al. in the PCTPublication Number WO2011/060047.

For another example, amino containing intermediates of formulaRfCH₂OCH₂CH(OH)CH₂O-A-O—CH₂CH(OH)CH₂NHCH₂CH₂CH₂Si(OMe)₃ can be formedthrough the reactions between glycidyl-containing compound of formula(IV), such as RfCH₂O—CH₂CH(OH)CH₂-L-CH₂-cyclo-CHCH₂O andNH₂CH₂CH₂CH₂Si(OMe)₃, as disclosed by Yokota, et al. in Eur. Pat. Appl.862068, using NH₂CH₂CH₂CH₂Si(OMe)₃ that is commercially available fromGelest, Inc., Morrisville, Pa. The intermediates of formulaRfCH₂OCH₂CH(OH)CH₂O-A-O—CH₂CH(OH)CH₂NHCH₂CH₂CH₂Si(OMe)₃ can be furtherreacted with allyl bromide or allyl chloride in the presence of KOH; andthen can be converted to the corresponding trichlorosilane through thereaction with HSiCl₃ in the presence of the Ashby's catalyst; andreacted with methanol to make the poly-silane compound of formula (I),exemplified by RfCH₂OCH₂CH(OCH₂CH₂CH₂Si(OMe)₃)CH₂O-A-O—CH₂CH(OCH₂CH₂CH₂Si(OMe)₃)CH₂NHCH₂CH₂CH₂Si(OMe)₃.

The fluorinated composition of formula (I) or formula (IV) may beapplied onto or contacted with a support surface by either wet coatingmethods or dry coating methods. Examples of dry coating methods includechemical vapor deposition (CVD) and physical vapor deposition (PVD).Examples of wet coating methods include dip coating, spray coating, spincoating, flow coating, roll coating, meniscus coating, and gravurecoating, etc.

When wet coating methods are employed, a suitable support surface is asolid surface containing functional groups that can form covalent bondswith the fluorinated silane (Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w). Suchfunctional groups include —OH, —COOH, —CHO, —Br, —Cl, —NH₂, —NHR, etc.,wherein R is a hydrocarbyl or a substituted hydrocarbyl. Preferably, thesupport surface has hydroxyl (—OH) groups on its surface. Examples ofsuch support surfaces include metal oxides, glass, silica, and anycombinations thereof. In some embodiments of this invention, the supportsurface is pre-treated to generate adequate functional groups, such ashydroxyl groups, on the surface. For example, a plastic surface may betreated with ozone to generate hydroxyl groups (Genzer, et al., Science2000, 290, 2130). In some embodiments of this invention, the supportsurface is a pre-treated plastic having hydroxyl groups on its surface.

When fluorinated glycidyl containing composition of formula (IV) isemployed, a suitable support surface is a solid surface containingfunctional groups that can form covalent bonds with the reactive epoxygroups. Such functional groups include —OH, —SH, —NH₂, —NHR, etc.,wherein R is a hydrocarbyl or a substituted hydrocarbyl. Preferably, thesupport surface has hydroxyl (—OH) or amino (—NHR) groups on itssurface. Examples of such support surfaces include glass and plastic. Insome embodiments of this invention, the support surface is pre-treatedto generate adequate functional groups, such as hydroxyl groups, on thesurface by treatment with ozone.

Typically, before contacting with the coating composition, the supportsurface needs to be cleaned and/or pre-treated using techniques known inthe art. For example, a support surface can be washed with a base suchas NaOH or KOH aqueous solution, rinsed with deionized water, washedagain with acid such as HCl or HNO₃, and then rinsed again withdeionized water followed with anhydrous methanol or ethanol and allowedto dry at elevated temperatures. Specific examples of support surfacepreparation are described in the Example section.

Generally, a solvent is required to dissolve the fluorinated compound offormula (I) or formula (IV) to make a coating solution for wet coatingmethods and some dry coating methods. Therefore, the coating compositioncomprises at least one solvent. The solvent can be fluorinated ornon-fluorinated. Suitable fluorinated solvents includehydrofluorocarbon, saturated hydrofluorocarbon ether, unsaturatedfluorocarbon ether, and mixtures thereof. Examples of hydrofluorocarboninclude saturated hydrofluorocarbon and hydrofluoroolefin. Examples ofsaturated hydrofluorocarbon ether include alkyl perfluoroalkyl ether.Examples of unsaturated fluorocarbon ether include unsaturatedhydrofluorocarbon ether. Examples of unsaturated hydrofluorocarbon etherinclude alkyl perfluoroalkene ether. In some embodiments of thisinvention, the at least one solvent is selected from the groupconsisting of saturated hydrofluorocarbon, hydrofluoroolefin, alkylperfluoroalkyl ether, alkyl perfluoroalkene ether, and combinationsthereof.

In some embodiments of this invention, the at least one solventcomprises, consists essentially of, or consists of a saturatedhydrofluorocarbon. Preferred saturated hydrofluorocarbons have normalboiling points of from about 50° C. to about 150° C. More preferredsaturated hydrofluorocarbons have normal boiling points of from about60° C. to about 120° C. In some embodiments of this invention, the atleast one solvent comprises, consists essentially of, or consists ofCF₃CHFCHFCF₂CF₃, i.e. Vertrel™ XF specialty fluid (CAS #138495-42-8,Chemours Company, Wilmington, Del.); or CH₃OC₄F₉, i.e. 3M™ Novec™Engineered Fluid HFE-7100 (3M, Minneapolis, Minn.).

Many of saturated fluorinated hydrocarbons have been found to contributeto global warming. Generally, unsaturated fluorocarbons have lowerglobal warming potentials (GWPs) than their saturated counterparts. Insome embodiments of this invention, the at least one solvent comprises,consists essentially of, or consists of an unsaturated fluorocarbon.Preferably, the at least one solvent comprises, consists essentially of,or consists of an unsaturated fluorocarbon having normal boiling pointof from about 50° C. to about 150° C. More preferably, the at least onesolvent comprises, consists essentially of, or consists of anunsaturated fluorocarbon having normal boiling point of from about 60°C. to about 120° C.

Examples of the unsaturated fluorocarbon include hydrofluoroolefins,alkyl perfluoroalkene ethers, and mixtures thereof. In some embodimentsof this invention, the at least one solvent comprises, consistsessentially of, or consists of a hydrofluoroolefin. Preferredhydrofluoroolefins have normal boiling points of from about 50° C. toabout 150° C. More preferred hydrofluoroolefins have normal boilingpoints of from about 60° C. to about 120° C.

In some embodiments of this invention, the at least one solventcomprises, consists essentially of, or consists of an alkylperfluoroalkene ether. Preferred alkyl perfluoroalkene ethers havenormal boiling points of from about 50° C. to about 150° C. Morepreferred alkyl perfluoroalkene ethers have normal boiling points offrom about 60° C. to about 120° C. In some embodiments of thisinvention, the alkyl perfluoroalkene ether is methyl perfluoroalkeneether, ethyl perfluoroalkene ether, or mixtures thereof. In someembodiments of this invention, the methyl perfluoroalkene ether ismethyl perfluoroheptene ether, methyl perfluoropentene ether, ormixtures thereof. Typically, methyl perfluoroheptene ether or methylperfluoropentene ether is a mixture of its isomers respectively. Forexamples, methyl perfluoroheptene ether may be a mixture comprisingCF₃CF₂CF═CFCF(OCH₃)CF₂CF₃, CF₃CF₂C(OCH₃)═CFCF₂CF₂CF₃, andCF₃CF═CFCF(OCH₃)CF₂CF₂CF₃. Methyl perfluoroheptene ether may also be amixture comprising CF₃CF₂CF═CFCF(OCH₃)CF₂CF₃, CF₃CF₂C(OCH₃)═CFCF₂CF₂CF₃,CF₃CF₂CF═C(OCH₃)CF₂CF₂CF₃, CF₃CF═CFCF(OCH₃)CF₂CF₂CF₃, andCF₃CF₂CF(OCH₃)CFHCF₂CF₂CF₃. Methyl perfluoropentene ether may be amixture comprising CF₃CF═C(OCH₃)CF₂CF₃, CF₃C(OCH₃)═CFCF₂CF₃, andCF₃CF═CFCF(OCH₃)CF₃.

Suitable non-fluorinated solvents include alcohols, ketones, nitriles,cyclic ethers, noncyclic ethers, and mixtures thereof. Preferably thenon-fluorinated solvent is selected from the group consisting ofalcohols, ketones, nitriles, cyclic ethers, noncyclic ethers, andmixtures thereof, wherein said non-fluorinated solvent has normalboiling point of from about 50° C. to about 150° C. More preferably, thenon-fluorinated solvent is selected from the group consisting ofalcohols, ketones, nitriles, cyclic ethers, noncyclic ethers, andmixtures thereof, wherein said non-fluorinated solvent has normalboiling point of from about 60° C. to about 120° C. In some embodimentsof this invention, the non-fluorinated solvent is selected from thegroup consisting of methanol, ethanol, proponal, isoproponal, acetone,methyl ethyl ketone, acetonitrile, tetrahydrofuran, and mixturesthereof. In some embodiments of this invention, the non-fluorinatedsolvent is selected from the group consisting of methanol, ethanol,proponal, isoproponal, and mixtures thereof.

Optionally, the coating composition containing formula (I) or formula(IV) also comprise at least one catalyst. The suitable catalystsfacilitate the covalent bond formation between the fluorinated silaneand fluorinated epoxide and the support surface. In some embodiments ofthis invention, the at least one catalyst comprises, consistsessentially of, or consists of acids, bases, or water. Examples of acidsinclude inorganic acids, alkyl sulfonic acids, halogenated alkylsulfonic acids, carboxylic acids, halogenated carboxylic acids, andmixtures thereof. Examples of inorganic acids include HCl, H₂SO₄, HNO₃,and mixtures thereof. Examples of carboxylic acids include formic acid,acetic acid, and mixtures thereof. Examples of bases include inorganicbases, substituted and unsubstituted trialkylamines, pyridine and itsderivatives, and mixtures thereof. Examples of inorganic bases includeNaOH, KOH, and mixtures thereof.

When a wet coating method is employed, the coating composition can beapplied to or contacted with the support surface using known techniquesto form a coating layer on the support surface. The support surfacetypically is cleaned and/or pre-treated as described above beforecontacting with the coating composition. The coated support surface isthen dried or cured at an elevated temperature. During the drying orcuring process, the solvents evaporate and the fluorinated silane(Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w) reacts with the support surface to format least one covalent bond with the support surface. For example, thefluorinated silane may form at least one Si—O-M bond with a metal oxidesupport surface, wherein M represents a metal. For another example, thefluorinated silane may form at least one Si—O—Si bond with a silicasupport surface. For another example, the fluorinated silane may form atleast one Si—O-M bond and/or at least one Si—O—Si bond with a glasssupport surface, wherein M represents a metal. In some embodiments ofthis invention, a fluorinated silane may form Si—O—Si cross-link bondwith an adjacent fluorinated silane. The coating may also comprise someunreacted or uncondensed Si—OH or Si-Q groups.

Typically, the coated support surface is dried or cured at thetemperature range of from about 18° C. to about 200° C. In someembodiments of this invention, the coated support surface is dried orcured at the temperature range of from about 18° C. to about 100° C.

In some embodiments of this invention, a coated article comprises,consists essentially of, or consists of (a) a support surface; and (b) acoating prepared by applying at least one fluorinated silane of theformula (I) (Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w) onto the support surface;wherein: Rf represents monovalentR¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d) wherein a, b, c, and dindependently represent an integer of from 3 to 200 inclusive, and thesum of a, b, c, and d is at least 1; R¹f is fluorinated alkyl group,linear or branched, with 1-4 carbons; Y represents a polyvalent organicgroup as defined above, Q represents a hydrolyzable group, a hydroxylgroup, or alkyloxy group capable of forming a siloxane bond with Siatoms located at the terminal of the molecular chain of formula (I) orother active sites of a treated surface; p is 1 or 2, and w is 2-14. Insome embodiments of this invention, the at least one fluorinated silaneis dissolved in at least one solvent before being applied onto thesupport surface.

In an aspect of the invention, the fluorinated silane of the formula (I)(Rf)_(p)-Y—(SiQ_(k)Z_(3-k))_(w) is represented by the formula

wherein e and m are an integer from 0 to 4, and e+m is at least 1, andwherein the at least one fluorinated silane moiety and the supportsurface are covalently bonded.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Measurement of Contact Angles Examples 1-6

All static contact angles were measured on a Ramé-Hart Model 590 F4Series Advanced Automated Goniometer with tilting base. The equippedsample pump was used to dispense a 10 μL liquid drop onto the preparedsurface of a substrate (support surface). The liquid drop was thenallowed to equilibrate for 10 seconds and a static contact anglemeasurement was taken using the DROPimage software included with theinstrument. This method was repeated a maximum of seven times down thelength of the glass slide. The average and the standard deviation, withBessel correction, for the measurements from each slide were thencalculated using the Microsoft Excel 2013 software.

The slides were then abraded with 0000 steel wool for 500 cycles andwater contact angle measured again. The abrasion test continued andwater contact angle was measured again after every 500 abrasion cyclesuntil the water contact angle dropped below 100°.

The term “roll-off angle”, as used herein, describes the angle at whichtranslation of the drop across the surface begins. The roll-off angle ismeasured on a Ramé-Hart Model 590 F4 Series Advanced AutomatedGoniometer. Using the tilting plate method. The measurement was madeusing a 10 μL liquid drop and tilting the base to 90°.

Slide Preparation Examples 1-6

The slides, VWR Micro Slides Superfrost® White and Generation 3 GorillaGlass, were placed in a glass vertical staining jar. A 2.5 M aqueoussodium hydroxide solution was poured into the jar so that the slideswere immersed up to the labeling section for 2.5 hours and then rinsedwith distilled water. The slides were then placed into a verticalstaining jar containing distilled water and were sonicated in anultrasonic bath for 10 minutes followed by immersion in 0.1 M aqueoussolution of hydrochloric acid for 10 minutes and finally distilled wateragain for 10 minutes. The slides were then soaked in anhydrous methanolfor 5 minutes. The slides were then dipped in a 0.2 wt % of fluorinatedsilane solution in HFE-7100 fluorocarbon solvent for 5 minutes. Theslides were then removed from the solution and placed in a slide holderto dry at 110° C. for 35 minutes. The slides were then buffed with aKimwipe™ to remove any residual material.

Preparation of Fluorinated Silanes

The following examples demonstrate the preparation of fluorinated silanesolutions according to the present invention.

Example 1

Perfluoro(poly)ether diallyl compoundF(C₃F₆O)_(n)—CF(CF₃)CH₂O—CH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂ (2.2 g, 0.54mmol, MW=4050, prepared according to the method described in the Journalof Fluorine Chemistry, 126 (2005) 281-288, from the correspondinghydroxy derivative), tetrahydrofuran (3.3 g), HFE-7100 solvent (5.5 g),platinum catalyst solution (0.026 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.0006 g), were placed in dried 100 mL 3-neck round bottomflask equipped with a cold water condenser, magnetic stirrer, heatingmantle, and thermocouple. HSiCl₃ (0.5 g, 3.8 mol) was added and thereaction mixture was heated to 56° C. during 20 hours. Conversion of 98%was achieved by the ¹H NMR analysis. The mixture was cooled to roomtemperature treated 3 times with excess of methanol, phase separated anddried in vacuum to afford 2 g ofF(C₃F₆O)_(n)—CF(CF₃)CH₂O—CH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃as white oil.

Example 2

Perfluoro(poly)ether poly-allyl compoundF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH═CH₂)—CH₂N[CH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂]-p-C₆H₃—OCH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂(1.56 g, 0.28 mmol, MW=5600), tetrahydrofuran (3 g), HFE-7100 (4 g),platinum catalyst solution (0.014 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.0004 g), were placed in 100 mL 3-neck round bottom flaskequipped with a cold water condenser, magnetic stirrer, nitrogenblanket, heating mantle, and thermocouple. HSiCl₃ (1.02 g, 7.5 mol) wasadded and the reaction mixture was heated to 53° C. during 16 hours.Additional C₁₂H₂₄O₄PtSi₄ catalyst (0.05 g of 0.1M solution), triphenylphosphine (0.0005 g), HSiCl₃ (0.8 g) was then added and the reactionmixture was heated at 50° C. during 24 hours. Complete conversion wasachieved by the ¹H NMR analysis. The mixture was cooled to roomtemperature treated with methanol (4.5 g), phase separated and dried invacuum to afford 1.02 g ofF(C₃F₆O)_(n)—CF(CF₃)CH₂O—CH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂N[CH₂CH(OCH₂CH₂CH₂—Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃]-p-C₆H₃—OCH₂CH(OCH₂CH₂CH₂—Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃as a yellow viscous oil.

Example 3

Perfluoro(poly)ether poly-allyl compound with main formulaF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH═CH₂)—CH₂O(CH₂)₄—OCH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂(3.19 g, 0.59 mmol, MW=5400, prepared according to the method describedin the Journal of Fluorine Chemistry, 126 (2005) 281-288, from thecorresponding hydroxy derivative), tetrahydrofuran (4 g), HFE-7100solvent (5.7 g), platinum catalyst solution (0.026 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.0007 g), were placed in 100 mL 3-neck round bottom flaskequipped with a cold water condenser, magnetic stirrer, nitrogenblanket, heating mantle, and thermocouple. HSiCl₃ (0.6 g, 3.5 mol) wasadded and the reaction mixture was heated to 55° C. during 20 hours.Complete conversion was achieved by the ¹H NMR analysis. The mixture wascooled to room temperature treated 2 times with excess of methanol,phase separated and dried in vacuum to afford 2.5 g ofF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂O—(CH₂)₄—OCH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃as clear oil.

Example 4

Perfluoro(poly)ether poly-allyl compoundF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂ (4.0 g, 0.96mmol, MW=5400, prepared according to the method described in the Journalof Fluorine Chemistry, 126 (2005) 281-288, from corresponding hydroxyderivative), tetrahydrofuran (5 g), HFE-7100 solvent (7 g), platinumcatalyst solution (0.2 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.005 g), were placed in 100 mL 3-neck round bottom flaskequipped with a cold water condenser, magnetic stirrer, nitrogenblanket, heating mantle, and thermocouple. HSiCl₃ (2.2 g, 16.7 mol) wasadded and the reaction mixture was heated to 58° C. during 20 hours.Complete conversion was achieved by the NMR analysis. The mixture wascooled to room temperature treated 3 times with excess of methanol,phase separated and dried in vacuum to afford 7.2 g ofF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃as clear oil.

Example 5

Perfluoro(poly)ether poly-allyl compound with main formulaF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH═CH₂)—CH₂O—CH₂C(CH₃)₂CH₂—OCH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂(2.64 g, 0.62 mmol, MW=4260), tetrahydrofuran (3.2 g), HFE-7100 solvent(4.7 g), platinum catalyst solution (0.029 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.0006 g), were placed in 100 mL 3-neck round bottom flaskequipped with a cold water condenser, magnetic stirrer, nitrogenblanket, heating mantle, and thermocouple. HSiCl₃ (0.6 g, 3.5 mol) wasadded and the reaction mixture was heated to 55° C. during 20 hours.More than 98% conversion was achieved by the ¹H NMR analysis. Themixture was cooled to room temperature treated 2 times with excess ofmethanol, phase separated and dried in vacuum to afford 1.25 g ofF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH₂CH₂—Si(OCH₃)₃)—CH₂O—CH₂C(CH₃)₂CH₂—OCH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃as white oil.

Example 6

Perfluoro(poly)ether poly-allyl compound with main formulaF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH═CH₂)—CH₂O—(CH₂)₄—OCH₂CH(OCH₂CH═CH₂)—CH₂OCH₂CH═CH₂(3.19 g, 0.59 mmol, MW=5440), tetrahydrofuran (3.8 g), HFE-7100 solvent(5.7 g), platinum catalyst solution (0.026 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.0007 g), were placed in 100 mL 3-neck round bottom flaskequipped with a cold water condenser, magnetic stirrer, nitrogenblanket, heating mantle, and thermocouple. HSiCl₃ (0.6 g, 3.5 mol) wasadded and the reaction mixture was heated to 55° C. during 20 hours.More than 95% conversion was achieved by the ¹H NMR analysis. Themixture was cooled to room temperature, treated 2 times with excess ofmethanol, phase separated and dried in vacuum to afford 2.5 g ofF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂O—(CH₂)₄—OCH₂CH(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂—Si(OCH₃)₃as clear oil.

Synthesis Example 7

Dry Perfluoro(poly)ether alcohol compound F(C₃F₆O)_(n)—CF(CF₃)CH₂OH (22g, 12.2 mmol, MW=1800), sodium methoxide (0.3 g), partially FluorinatedAlcohol Substituted Glycol Capstone™ FS-3100 (0.23 g, available fromChemours), were placed in 100 mL 3-neck round bottom flask equipped witha cold water condenser, magnetic stirrer, heating mantle, andthermocouple under nitrogen and heated in vacuum at 40-45° C. for 15minutes. After methanol was removed, tetrabutyl ammonium iodide (0.06 g)and 1,4-butanediol diglycidyl ether was added (2.84 g, purchased fromAldrich) to the flask at 70° C., and then heated to 100° C. for 6 hours.After addition of sodium hydride (0.1 g), and additional heating to 100°C. for 10 hours 95% conversion was achieved. The unreacted diglycidylether was extracted with tetrahydrofuran and product was dried in vacuumto affordF(C₃F₆O)_(n)—CF(CF₃)CH₂O—CH₂CH(OH)—CH₂O—(CH₂)₄—OCH₂-cyclo-CHCH₂O (18.3g) as yellow oil.

Comparative Synthesis Example 1

Perfluoro(poly)ether poly-allyl compound with main formulaF(C₃F₆O)_(n)—CF(CF₃)CH₂OCH₂CH═CH₂ (7.0 g, 1.36 mmol, Mn=5140, preparedaccording to the method described in the Journal of Fluorine Chemistry,126 (2005) 281-288, from the corresponding hydroxyl derivativeF(C₃F₆O)_(n)—CF(CF₃)CH₂OH), tetrahydrofuran (7 g), HFE-7100 solvent (9g), platinum catalyst solution (0.064 g of 0.104 Mplatinum-2,4,6,8-tetramethyl-2,4,5,8-tetravinylcyclotetrasiloxanecomplex in methylvinylcyclosiloxanes, purchased from Aldrich), triphenylphosphine (0.0015 g), were placed in 100 mL 3-neck round bottom flaskequipped with a cold water condenser, magnetic stirrer, nitrogenblanket, heating mantle, and thermocouple. HSiCl₃ (0.74 g, 5.5 mol) wasadded and the reaction mixture was heated to 55° C. during 20 hours.More than 98% conversion was achieved by the ¹H NMR analysis. Themixture was cooled to room temperature treated 2 times with excess ofmethanol, phase separated and dried in vacuum to affordF(C₃F₆O)_(n)—CF(CF₃)CH₂O—CH₂CH₂CH₂Si(OCH₃)₃ (6 g) as clear oil.

Tables 1-4 demonstrate the effectiveness of using fluorinated silanesolutions in fluorinated solvent prepared according to the presentinvention on the surface of two types of glass, Super Frost White(Tables 1 and 2) and Gorilla Glass (Tables 3 and 4).

Water contact angle (WCA) measurements on Super Frost White glass slideswere measured as described above and are shown in Tables 1 and 2.

TABLE 1 Abraded Abraded Abraded Abraded Abraded WCA (°) WCA (°) WCA (°)WCA (°) WCA (°) Roll-off Initial (500 (1000 (1500 (2000 (2500 ExampleNo. angle (°) WCA (°) cycles) cycles) cycles) cycles) cycles)Comparative 4.6 116.2 112.1 102.8 100.2  93.9 — Example 1 Example 1 —117.5 112.7 109.9 106.6 106.3  96.0 Example 2 8.8 117.8 109.3 107.6105.4  99.5 — Example 3 7.2 115.1 110.2 99.5 — — — Example 4 14.6 112.1112.0 108.7 113.3 110.9 105.4 Example 5 5.8 115.1 105.4 95.0 — — —Example 6 6.4 114.1 109.9 106.4  94.0 — — “—” - no measurement wasperformed.After drying or curing process described above the glass slides werewiped with Ethanol-wipe and water contact angle (WCA) measurements weredone as described above and are shown in Table 2

TABLE 2 Abraded Abraded Abraded Abraded Abraded WCA (°) WCA (°) WCA (°)WCA (°) WCA (°) Roll-off Initial (500 (1000 (1500 (2000 (2500 ExampleNo. angle (°) WCA (°) cycles) cycles) cycles) cycles) cycles)Comparative 11.2 115.2 110.5 102.7 99.1 — — Example 1 Example 1 8.8117.1 111.5 103.8 96.6 — — Example 2 6.0 114.1 107.1 105.2 94.9 — —Example 3 9.0 111.3 106.7  84.5 — — — Example 4 7.6 112.4 107.9 106.6108.7  106.1 103.2 Example 5 7.0 113.8 93.3 — — — — Example 6 5.4 115.5110.3 108.9 87.6 — —

Water contact angle (WCA) measurements on Gorilla Glass were measured asdescribed above and are shown in Tables 3 and 4.

TABLE 3 Abraded Abraded Abraded Abraded WCA (°) WCA (°) WCA (°) WCA (°)Roll-off Initial (500 (1000 (1500 (2000 Example No. angle (°) WCA (°)cycles) cycles) cycles) cycles) Comparative 8.8 115.0 107.3 85.2 — —Example 1 Example 1 7.0 115.9 113.2 99.3 — — Example 2 8.0 113.7 89.5 —— — Example 3 7.8 112.5 86.4 — — — Example 4 11.4 113.5 112.2 111.1 109.5 95.7 Example 5 8.0 113.5 106.0 89.1 — — Example 6 5.6 115.2 112.096.4 — —

After drying or curing process described above the Gorilla Glass slideswere wiped with Ethanol-wipe and water contact angle (WCA) measurementswere done as described above and are shown in Table 4.

TABLE 4 Abraded Abraded Abraded Abraded Abraded WCA (°) WCA (°) WCA (°)WCA (°) WCA (°) Roll-off Initial (500 (1000 (1500 (2000 (2500 ExampleNo. angle (°) WCA (°) cycles) cycles) cycles) cycles) cycles)Comparative 5.4 117.3 114.3  85.0 — — — Example 1 Example 1 6.4 117.199.3 — — — — Example 2 7.6 114.8 91.2 — — — — Example 3 5.4 114.7 78.1 —— — — Example 4 5.8 115.5 109.7 107.1 106.8 100.7 102.1 Example 5 6.4116.2 93.1 — — — — Example 6 5.2 116.4 82.1 — — — —

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification is to be regarded in anillustrative rather than a restrictive sense, and all such modificationsare intended to be included within the scope of invention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.

What is claimed is:
 1. A coating composition comprising: at least onefluorinated silane of the formula (I):(Rf)_(p)—Y—(SiQ_(k)Z_(3-k))_(w)  (I) wherein: Rf represents monovalentR¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d) wherein a, b, c, and dindependently represent an integer of from 3 to 200 inclusive, and thesum of a, b, c, and d is at least 1; R¹f is fluorinated alkyl group,linear or branched, with 1-4 carbons; Y represents a polyvalent organicgroup that enables branching and can contain polyvalent alkyl, divalentpolysiloxane, p-, m-, or o-phenylene; Y contains at least 2 or more ofthe heteroatom containing groups selected from: —O—, —S—, —NR²—,—C(O)O—, C(O)NR²—, where R² is covalent bond, divalent alkylene,hydrogen, methyl, ethyl or isopropyl; Q represents a hydrolyzable group,a hydroxyl group, or alkyloxy group, Z represents a monovalent alkylgroup such as methyl, ethyl, propyl, butyl, phenyl group, or hydrogen, pis 1 or 2, w is 2-14, p+w is 3 to 15, and k is from 1 to
 3. 2. Thecomposition of claim 1 wherein the fluorinated silane has the formulaF(C₃F₆O)_(n)—CF(CF₃)CH₂—O—[—CH₂CH(—OC₃H₆Si(OCH₃)₃)CH₂—O—]_(e)—[CH₂CH(—CH₂OC₃H₆Si(OCH₃)₃)O—]_(m)—C₃H₆—Si(OCH₃)₃,wherein e and m are independently integers from 0 to 4, and e+m is atleast 1, and n is an integer from 7 to
 100. 3. The composition of claim1 wherein the fluorinated silane has the formulaF(C₃F₆O)_(n)—CF(CF₃)CH₂O—CH₂CH—(OCH₂CH₂CH₂Si(OCH₃)₃)—CH₂OCH₂CH₂CH₂Si(OCH₃)₃,and n is an integer from 7 to
 100. 4. The coating composition of claim 1wherein the Rf— is C₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, n is an integer from7 to 100, and Y is—CH₂OCH₂CH(OCH₂CH₂CH₂—)CH₂O-p-C₆H₄—N[CH₂CH(OCH₂CH₂CH₂—)CH₂OCH₂CH₂CH₂—]₂.5. A coating composition comprising: at least one fluorinated silane ofthe formula (IV):

wherein: Rf represents monovalentR¹f(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d) wherein a, b, c, and dindependently represent an integer of from 3 to 200 inclusive, and thesum of a, b, c, and d is at least 1; R¹f is fluorinated alkyl group,linear or branched, with 1-4 carbons; L is a divalent or trivalent groupcontaining at least 1 of the following heteroatoms —O—, —S—, and —N<, jis from 1 to 2, and p is from 1 to
 2. 6. The coating composition ofclaim 5 wherein the Rf— is C₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, and n is aninteger from 7 to
 100. 7. The coating composition of claim 6 wherein theL is —OCH₂CH₂CH₂CH₂O—.
 8. The coating composition of claim 6 wherein theL is